Article

One- and Two-Photon Photochemistry and Photophysics of Poly(arylenevinylene)s Containing a Biphenyl Moiety

  1. Veronika Strehmel Dr.1,
  2. Ananda M. Sarker Dr.2,
  3. Paul M. Lahti Prof. Dr.2,
  4. Frank E. Karasz Prof. Dr.2,
  5. Matthias Heydenreich Dr.1,
  6. Hendrik Wetzel Dr.3,
  7. Sophie Haebel Dr.1,
  8. Bernd Strehmel Priv.-Doz. Dr.1,4

Article first published online: 4 FEB 2005

DOI: 10.1002/cphc.200400407

Issue

ChemPhysChem

ChemPhysChem

Volume 6, Issue 2, pages 267–276, February 11, 2005

Additional Information

How to Cite

Strehmel, V., Sarker, A. M., Lahti, P. M., Karasz, F. E., Heydenreich, M., Wetzel, H., Haebel, S. and Strehmel, B. (2005), One- and Two-Photon Photochemistry and Photophysics of Poly(arylenevinylene)s Containing a Biphenyl Moiety. ChemPhysChem, 6: 267–276. doi: 10.1002/cphc.200400407

Author Information

  1. 1

    University of Potsdam, Institute of Chemistry, Interdisciplinary Research Center for Biopolymers, Karl Liebknecht Str. 24/25, 14476 Potsdam-Golm, Germany, Fax: (+49) 331-977-5036

  2. 2

    University of Massachusetts at Amherst, Department of Polymer Science and Engineering, Department of Chemistry, Amherst, MA01003, USA

  3. 3

    Fraunhofer Institute for Applied Polymer Research, Geiselbergstr. 69, 14476 Potsdam-Golm, Germany

  4. 4

    Kodak Polychrome Graphics, Research and Development, An der Bahn 80, 37520 Osterode am Harz, Germany, Fax: (+49) 5522-997-577

Publication History

  1. Issue published online: 4 FEB 2005
  2. Article first published online: 4 FEB 2005
  3. Manuscript Revised: 31 OCT 2004
  4. Manuscript Received: 27 AUG 2004

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Keywords:

  • conjugation;
  • fluorescence;
  • photochemistry;
  • photophysics;
  • two-photon absorption

Graphical Abstract

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Two-photon absorption of conjugated oligomers: Two-photon (TP) excitation of poly[(2,5-alkyloxy-p-phenylenevinylene)alt-(biphenylenevinylene)] (see figure) results in a TP absorption cross-section of >200 GM (GM=Göppert–Mayer units) if R=O[BOND]Alkyl, whereas less TP absorptivity is observed when R=H. The Strickler–Berg relation was applied to evaluate the effective conjugation length as a quantity that reliably contributes to the photonic properties determined.

Abstract

Photochemical and photophysical properties were investigated for poly(arylenevinylene)s containing a flexible biphenyl “hinge” unit by applying one-photon (OP) and two-photon (TP) excitation to explore excited-state properties. The poly(arylenevinylene)s were poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(4,4′-dihexyloxy-3,3′-biphenylenevinylene)] (1), poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2′-dihexyloxy-3,3′-biphenylenevinylene)] (2), and poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2′-biphenylenevinylene)] (3). Effective emission quantum yields and related photonic properties were evaluated on a realistic per-chromophore basis using effective conjugation lengths based on the Strickler–Berg relationship. Intramolecular photocyclization was deduced to occur in the one case where the biphenyl molecular connectivity permitted the reaction, based on matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF), heteronuclear multiple-quantum coherence (HMQC)-NMR, and gel-permeation chromatography (GPC) results. The various photoprocesses could be induced by either OP or TP excitation, though the first excited singlet state is the photoactive state. The higher excitation energy of the TP excited state favors indirect population of the S1 state by electronic coupling between the TP and OP excited states [λequation image (nm): 726; δ (GM)9: 1=229, 2=215, 3=109). Photochemical processes occurring from the lowest OP excited state (S1) could therefore also be indirectly induced by TP excitation.

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